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2005, 44, 6729-6740
Novel Reactor Temperature and Recycle Flow Rate Policies for Optimal Process Operation in the Plantwide Context
Jeffrey D. Ward, Duncan A. Mellichamp, and Michael F. Doherty*
Department of Chemical Engineering, University of California, Santa Barbara, California 93106-5080
Ward et al. (Ward, J. D.; Mellichamp, D. A.; Doherty, M. F. Ind. Eng. Chem. Res. 2004, 43, 3957) investigated the effect of process chemistry on the selection of the operating policy for plants with recycle. This paper extends that work to consider the possibility of reactor temperature as a degree of freedom in plantwide process operation. It is possible to predict, based on the process chemistry, when it may be appropriate to implement a variable-temperature operating policy, and, alternatively, when a constant-temperature operating policy is appropriate in the face of a production rate change or other disturbances. An interesting and nonobvious result is also developed: For so-called bounded chemistries, it is usually optimal to operate the process with the reactor at its high-temperature constraint, even if the activation energy of the undesired reaction is greater than the activation energy of the desired reaction. This means that the plantwide operating policy is the same for almost all bounded chemistries. In contrast, for nonbounded chemistries, the operating policy follows conventional wisdom and changes depending on the relative magnitude of the activation energies. Implications of the optimization analysis for control structure design are also discussed.
1. Introduction The influence of reactor temperature on the selectivity and yield of a reactor network is well-known and is discussed by many authors and in many textbooks on reactor design; e.g., Fogler2 and Levenspiel.3 For example, for the case of one desired reaction and one undesired reaction, where the rates of reaction are temperature dependent via the Arrhenius equation ted to change. Several authors have noted6,8 that another possible way of accommodating a production rate change is to vary the reactor temperature. Monroy-Loperena et al.9 recently considered the use of reactor temperature as a degree of freedom for a parallel control structure. However, the chemistry under investigation by all of these authors (A f B) does not represent the most general case, because there is no downside to a temperature increase. If a production rate increase is desired, then the reaction rate constant k can simply be increased (via the reactor temperature) so that the rate of production of the desired product is increased while maintaining the same reactor holdup and recycle flow rates. In many cases, however, there is a downside to increasing the reactor temperature, namely that an undesired reaction may experience a rate increase that is greater than that for the desired reaction. In this case, the issue of how reactor temperature should be employed as part of a plantwide operating policy is not so clear. Furthermore, in some cases the reactor temperature operating policy may influence the level/flow rate policy, because lower temperatures generally require longer reactor residence times and therefore greater reactor holdup. The purpose of this paper is to extend the analysis of Ward et al.1 to include the use of reactor temperature as an independent variable in the selection of an operating policy. Because this work is an extension of results presented in a previous paper, the reader may find it useful to refer to that paper for background information. It is shown in the present work that the problem of selecting a plantwide operating policy is different from the problem of designing a reactor network, and in some instances the intuition that is developed from the point of view of plantwide operation is radically different from the intuition that is developed from the reactor network design perspective. For ex-
k ) k0e-EA/RT
and the desired reaction has an activation energy greater than the undesired reaction, then both selectivity and yield are improved by operating the reactor at high temperature. If the activation energy condition is reversed, then selectivity is improved by operating at lower temperature, but yield may be reduced because both reactions will proceed more slowly. What is less well-known, but even more important, is what role the reactor temperature should play as an independent variable in plantwide optimization. There has been considerable discussion in the literature about the choice of a plantwide inventory/flow operating policy (and control structure) for plants with recycle. As discussed by Ward et al.1 the chemistry of the process under investigation plays a critical role in the proper selection of a plantwide operating policy. This work considered plants which are operated with a constant reactor temperature. A critical question in the selection of a plantwide operating policy is how to accommodate a production rate change. Luyben4 recommends that recycle flow rates be held constant, Skogestad and coworkers5,6 recommend that reactor holdup be held constant, and Yu and co-workers7,8 recommend that both the reactor level and recycle flow rates be permit* To whom correspondence should be addressed. mfd@ engineering.ucsb.edu.
10.1021/ie0491589 CCC: $30.25 © 2005 American Chemical Society Published on Web 07/13/2005
2005 process optimizer may be required to supervise the decentralized regulatory control structure.12 as a basis for designing distributed feedback control structures for chemical processes. which will be inactive. Table 1. hereafter called chemistry 1 (Table 1) r0 ) k0[A][B] r1 ) k1[A]2 r0 ) k0[A][B] r1 ) k1[A][C] r0 ) k0[A][B] r1 ) k1[C]2 r0 ) k0[A][B] r1 ) k1[C] r0 ) k0[A][B] r1 ) k1[A]2 r2 ) k2[C]2 r0 ) k0[A] r1 ) k1[C] r0 ) k0[A] r1 ) k1[A]2 r0 ) k0[A][C] r1 ) k1[A]2 r0 ) k0[A]2 r1 ) k1[A][C] r0 ) k0[A][C] r1 ) k1[A]2 r2 ) k2[C]2 Figure 1. Therefore. Therefore. The analysis presented in this paper provides insight into whether a self-optimizing control structure will be adequate to achieve good economic performance of the process. and RB ) ′ ′ ′ ′ RB/PC. RA ) RA/PC. PD ) PD/PC. The idea behind self-optimizing control is to select variables for control which. Review of Previous Results. then a centralized q ) RAvA + RBvB + PCvC + PDvD (5) where vA is the molar volume of species A. then it is straightforward to design a self-optimizing control structure. If one or more optimization variables lie away from constraints and move considerably as properties of the process change.1.1 The reader may wish to refer to this paper for further details. Recently. and the following process chemistry. Vol.6730 Ind. it is shown here that for bounded chemistries. Maarleveld and Rijnsdorp10 were among the first authors to recognize that it is often the case that the optimal operating point for a process is at a constraint rather than at the “hilltop”. The process variables selected for control are those that lie on the constraints. For this chemistry. because a large excess of species B suppresses the undesired reaction. 44. even if the activation energy of the undesired reaction is greater than the activation energy of the desired reaction. Reaction rate constants are made dimensionless by dividing by the rate constant of the desired reaction. it is necessary to express the byproduct production rate PD in terms of these degrees of freedom. it is seen that PC ) k0[A][B]V PD ) k1[A]2V (3) (4) The concentrations of species A and B in the reactor can be replaced by recycle flow rates by introducing the reactor effluent volumetric flow rate q ample. or if the active constraints are expected to shift over the range of process operation. Chem.. Thus V PC ) k0RARB 2 q V PD ) k1R 2 2 A q (6) (7) Dividing the expression for the undesired reaction by the expression for the desired reaction gives k1R 2 k1RA PD A ) ) PC k0RARB k0RB (8) Flow rates are made dimensionless by dividing them by the production rate of the desired product. Eng. in dimensionless form ′ ′ P D ) k1 RA ′ RB ′ (9) where k1 ) k1/k0. PC. etc. Consider the process flow diagram shown schematically in Figure 1. self-optimizing control has been advocated by several authors11. PD f 0 as RA f 0. . Methodology 2. No. This section briefly reviews results that were presented in Ward et al. and which may switch during operation as the production rate is changed. If the optimal operating point for a plant always lies at the intersection of the same constraints. From a global steady-state material balance. Generic process flow diagram. when kept near their setpoints. reflecting the fact that byproduct production rate becomes small in the limit of high per-pass conversion of species A. RA and RB. Res. Chemistries 1 2 3 4 5 6 7 8 9 10 A+BfC A+AfD A+BfC A+CfD A+BfC C+CfD A+BfC CfD+E A+BfC A+AfD C+CfE AfC CfD AfC A+AfD A + C f 2C A+AfD A+AfC A+CfD A + C f 2C A+AfD C+CfE A+BfC A+AfD r0 ) k0[A][B] r1 ) k1[A]2 desired undesired (2) The independent variables for the economic optimization are the recycle flow rates of species A and B. or as RB f ∞. it is usually optimal to operate the process with the reactor at its high-temperature constraint. and if so how such a control structure should be designed. keep the process near to its economic optimum over the expected range of disturbances. 2. 17. The operating policies that are developed specify which process constraints will be active.
0 (14) It is assumed here that all EA. CD is the cost of producing one mole of undesired byproduct (including raw materials costs and separations costs) (CD > 0). Generally speaking. i. the term CC PC is constant and its value will affect the value of the total profit but not the location of the minimum cost. 17.CC ) CD PD + (RA + RB ′ ′ ′ ′ ′) PCCR V′ ) (13) Vk0.e. including to undesired reactions with a different overall reaction order than the desired reaction.3.1 2. therefore. then k1 ′ will be a function of temperature ′ k1 ) k1/k0 ) k1.1 > EA.1-EA. the result for chemistry 3 ′ k1 ) k1/k0 ) k1.i are temperature independent. it is usually the case for profitable process ′ operation that PD . The simplest model for the economic potential of a chemical plant that will capture the tradeoff between recycle costs and byproduct production costs is ′ If EA. One consequence is that a typical value of the dimensionless temperature T′ is small. species A and B are symmetric (interchangeable).1). ′. In our previous paper. 2.. A dimensionless temperature is defined based on the activation energy of the desired reaction Note that with variable reactor temperature. Res. Because PC is fixed. and q′ is the dimensionless reactor effluent volumetric flow rate q′ ) q PC vC ) vA A + vB B + 1 + vD D ′R ′ ′R ′ ′P ′ (18) where v′i ) vi/vC. CD is a relatively large number. this process has three independent operational degrees of ′. T′ ) RT/EA. Therefore the dimensionless reactor volume defined in this way is also a large number.Ind. However. and plug flow reactors (Ward et al.0 vC2PC ) e1/T′ 2 q′ RA B ′R ′ (20) where CD is the ratio of the cost of producing one mole ′ of byproduct to the cost of recycling one mole of reactant species. These results have important implications for the plantwide optimization problem. the following dimensionless cost objective function is defined where vC is the molar volume of the desired product C. CC is the negative of the revenue from the production of one mole of desired product (CC < 0). Therefore. equilibrium reactions. eq 14 becomes . every process variable has an upper and lower bound.0 e-1/T′ vC PC 2 ) 1 q′2 RA B ′R ′ (19) and. Note that for many liquid-phase chemistries. This methodology can be generalized in a number of ways. then q′ will be essentially independent of temperature. RB) + CR(RA + RB) (12) where C is the cost of operating the plant (smaller values of C imply larger profit).1 > 1. the following result was developed for chemistry 1 Vk0 v2 PC C ) 1 q′2 RA B ′R ′ (17) C ) CC PC + CD PD(RA. Typically. the dimensionless reactor volume is C′ ) C . Therefore. 1. Chem. the plant is at its most profitable operating point. 2005 6731 By contrast. Vol. Therefore. multiple undesired reactions.0 e(1-EA. When C ′ is minimized. the reactor holdup required to achieve a given production rate will decrease as the reactor temperature is increased. The explanation is that only a small fraction of intermolecular collisions have enough energy to overcome the energetic barrier and react to form products. EA/(RT) > 10. on ′ the order of 100. the activation energy is an order of magnitude or more greater than the average thermal energy of the molecules in solution. 44.0 then EA. PD f 0 if either RA f ∞ or RB f ∞. Results This section presents the optimization landscapes for a variety of process chemistries. 3. freedom: RA RB and T′.. Eng. the exponent in eq 16 will ′ have a negative value.1)/T′ ′ ′ (16) A+BfC C+CfD is r0 ) k0[A][B] r1 ) k1[C]2 desired undesired (10) ′ PD ) k1 k1 ′ ′ 1-2 RA RB ′ ′ RA RB ′ ′ ( ) -1 ≈ k1 ′ RA R B ′ ′ (11) In this case. typically V′ > 106. and dimensionless reactor volume V′ will depend on the dimensionless temperature T′ only via the exponential term (and not by q′). Note also that for most liquid-phase chemistries the Arrhenius factor k0 is typically a large number.0)/RT e k0. Byproduct Production Rates with Variable Reactor Temperature.0 (15) Activation energies and Arrhenius preexponential constants are rendered dimensionless by dividing by the corresponding quantity for the desired reaction. It is important to bear in mind the nature of the constraints which may become active during process operation. Reactor Volume with Variable Reactor Temperature. then Vk0. No. In eq 20. q′ is a function of T′ ′ ′) ′ (as well as RA and RB because PD is a function of T′. In this case.2. If this is the case. If the reactor temperature is available as an operational degree of freedom. and CR is the cost of separating and recycling one mole of reactant species (CR > 0). If the reaction rate constant is temperature dependent via the Arrhenius equation. The per-pass conversion of both species should be kept low to dilute the product species C and suppress the undesired reaction. conventional wisdom suggests that increasing the reactor temperature favors the production of byproduct species. and k1 will increase with increasing temperature. usually T′ < 0.0 -(EA.
depending on the relative magnitude of the activation energies and the ratio of the exponents in the kinetic rate expressions. × marks the optimal operating point. a selfoptimizing control structure could be designed which keeps constant both the reactor temperature (at the . which are guaranteed to be inactive. × marks the optimal operating point. We have assumed that the lower bound on the reactor temperature is constant independent of the production rate or the operating point. EA. For a process chemistry of this type. Figure 2. ′ ′ 3.1 < 1. then the process should be operated with reactor level proportional to production rate. Figure 2 illustrates the optimization problem for chemistry 6. For reference. The optimal operating point is on the high temperature constraint. Table 2 summarizes the operating policy for each class of process chemistry on the basis of which constraints are guaranteed to be active.1. × marks the optimal operating point. the recycle flow rate scales linearly with the production rate. Chemistry 6 (nonbounded chemistry) with EA. a nonbounded chemistry. Res.1 < 1 after ′ production rate increase. and which may switch during process operation. the upper bound may be given by safety considerations.1 < 1 after ′ production rate increase. the area available for heat transfer in the reactor. In this case. then the process should be operated with the reactor completely full.1 < 1. Figure 3. or the limits of a refrigeration system.3 there are certain cases where this heuristic is not be valid. 2005 Table 2. Chemistry 7 (bounded chemistry) with EA.1 < 1 before ′ production rate increase.6732 Ind. max may switch may switch may switch Tmin may switch inactive Tmax inactive active a Note: following the analysis of Section 3. max inactive inactivea inactive Tmin inactivea inactive Tmax activea active Vmax may switch may switch inactive nonbounded RA. This policy will simultaneously maximize the process selectivity (by minimizing the ratio of reaction rate constants) and minimize the required reactor holdup. the reactor temperature should be held constant at the upper limit. This assumption will generally be conservative if the lower bound is calculated for the maximum possible production rate. No. Chemistry 7 (bounded chemistry) with EA. the lower bound may. The reactor temperature policy does not influence the level/flow policy in this case: if the overall process chemistry is bounded. Chem. Eng.1 < 1 ′ Vmax active activea active bounded RA. Because this heuristic has been derived. × marks the optimal operating point. The least interesting case is when EA. and away from the reactor volume constraint. 44. Chemistry 6 (nonbounded chemistry) with EA.. as suggested in our previous paper.3 when it is valid and when it is not. values of dimensionless groups in Figures 2-10 are shown in Table 3. Vol. coking or catalyst degradation.1 < 1 ′ before production rate increase. for example. 17.1 > 1 ′ EA. A production rate increase (Figure 3) does not change either the optimal operating temperature or optimal dimensionless recycle flow rate. This situation corresponds to an operating policy where Figure 4. or the limits of materials of construction. Summary of Derived Heuristics for Plantwide Operating Policy Based on Active/Inactive Constraints for Processes with One Recycle Stream chemistry: constraint: isothermal EA. if the overall process chemistry is nonbounded. Figure 5. be given by the cooling water approach temperature. For reactor temperature. it is possible to determine following the analysis of Section 3.
8 0. Therefore. Chemistry 7 (bounded chemistry) with EA.2 Vmax ′ 3 × 105 2 × 105 3 × 107 2 × 107 1. When the production rate is increased (Figure 5).53 0. × marks the optimal operating point.. the location of the optimal operating point shifts to the new intersec- tion of the reactor volume constraint and the high temperature constraint. Chemistry 6 (nonbounded chemistry) with EA.08 0.9 0. EA. Chem.5 0.2 1. Table 3.25 0. the reactor holdup must increase.1 ′ 0. × marks the optimal ′ operating point.Ind. However. then low reactor temperatures will minimize the reaction rate constant ratio k1. Such a control structure would keep the process at its optimal operating point over the entire possible range of production rates.1 0. ′ ′ 3. Figure 9. However. for a non′ bounded chemistry. and the reactor holdup constant (at the maximum value).1 > 1 before ′ production rate increase. as argued earlier (eq 20). 2005 6733 Figure 6. Chemistry 8 (bounded chemistry) with EA.8 0.1 > 1 after ′ production rate increase.8 × 108 0.1 > 1. Chemistry 6 (nonbounded chemistry) chemistry with EA. A supervisory control structure with a mechanism for constraint handling may be required to operate the process most profitably over the entire range of production rates.2. Figure 7.9 0.2 1. as the temperature is decreased with fixed recycle flow rates. Furthermore. a self-optimizing control structure would be relatively easy to design and implement. For chemistries of this type.1 > 1 ′ before production rate increase.1 > 1 after production rate increase.53 4. at all times either the low-temperature constraint or the maximum reactor holdup constraint . 17. No. × marks the optimal operating point. such a control structure would only work properly in the region of production rates where the maximum recycle flow rate constraint was inactive.max ′ 9 4. it is not desirable to maximize the per-pass conversion of any species. 44. This situation corresponds to an operating policy in which both the reactor temperature and the reactor holdup are kept constant at their maximum values at all times. The optimal operating point lies at the intersection of the high temperature constraint and the reactor volume constraint. Values of Dimensionless Groups in Figures figure 2 3 4 5 6 7 8 9 10 chemistry 6 6 7 7 6 6 7 7 8 CD ′ 100 100 100 100 100 100 100 100 100 k1.1 1 1 1 1 1 EA. The control structure would keep the reactor temperature constant (at the high-temperature constraint). Chemistry 7 (bounded chemistry) with EA.5 2.53 Figure 8. 0 ′ 0.9 1. × marks the optimal operating point. Figure 4 shows the optimization landscape for chemistry 7. Figure 10.1 > 1.2 1.2 1. Nonbounded Chemistry. If EA. Vol.1 > 1 after ′ production rate increase.08 0. high temperature constraint) and the ratio of the recycle flow rate to the production rate. a bounded chemistry.9 0. × marks the optimal operating point. Eng. Res.9 × 108 3 × 107 2 × 107 2 × 107 R A.
lowering the temperature will ′ decrease the rate of both reactions and therefore limit the per-pass conversion in the reactor. which increases the reaction rate constant ratio k1.1 > 2. where it is not desirable to make the perpass conversion as high as possible. as shown in Figure 7.1 ) 1.0 e(1-EA. until the high temperature constraint or recycle flow rate constraint becomes active and finally the process becomes inoperable as the feasible region shrinks to zero and the desired production rate can no longer be achieved. it is expected that the optimal operating policy will require operation with the reactor completely full at all times. Res.1)/T′ ′ ′ e V′max (28) AfC A+AfD r0 ) k0[A] r1 ) k1[A]2 desired (21) undesired (22) and the case where EA1 ) EA1/EA0 > 1.1 > 1. This is in contrast to the case of a nonbounded ′ chemistry. Thus.1)/T′ (27) and therefore PD ) ′ k1. it would be difficult to design a selfoptimizing control structure. and therefore it is not desirable to operate on the high-temperature constraint.6734 Ind. It is possible that the active constraint (low temperature or reactor holdup) may switch during operation as the production rate is changed or other disturbances are encountered. Consider chemistry 7 From previous results.3. while the minimum temperature constraint becomes inactive. inhibiting the ability of the system to suppress the undesired reaction by driving the concentration of the reactor-volume bounded species (A) to zero. since ′ EA. Therefore.1 < 1. but not both. In the remainder of this section. Since the maximum reactor holdup is fixed. Vol. Chem. Under this assumption. The undesired reaction is suppressed more effectively at higher temperatures because higher temperatures maximize conversion and reduce the concentration of the bounded species. unless EA. ′ It was just a coincidence that all of the terms of RA ′ and q′ canceled out in the expression for PD (eq 26). This result is exactly the opposite of what would be expected on the basis of activation energies alone. because the ′ process chemistry is bounded. In contrast. the reactor temperature is not nondimensionalized by the production rate. analytical results are developed for several other process chemistries in this category (EA. however the same constraints remain active.1 > EA. No. away from the reactor volume constraint. decreasing the reactor temperature will improve the ratio of the reaction rate constants (decrease k1). which reduces the rate of byproduct formation. it is straightfor′ ward to design a self-optimizing control structure. 17. these two competing effects give rise to a surprising result that contradicts the conventional wisdom regarding reactor temperature operating policy. For ′ an example where such cancellation is not exact. EA. as for the case of a bounded chemistry with EA.1 > 1. an increase in the production rate causes these constraints to shift. However. as the production rate is increased. In this case. it is usually best to maximize the per-pass conversion of the bounded species (minimize the recycle flow rate of that species) even at the expense of operating at high temperature. 2005 will be active. Generally. as a result of competing contributions to the selectivity. 44. Because the reactor volume and recycle flow rate constraints are nondimensionalized by dividing by the production rate PC. 3. we can write ′ RA e1/T′ ) q′ Vmax ′ and (25) ′ ′ P D ) k1 however note that e1/T′ Vmax ′ (26) ′ ′ ′ k1 ) k1. An increase in the production rate of 50% (Figure 9) shrinks the feasible region. the process should be operated with the reactor volume completely full at all times. . because there are two constraints which may switch during the course of process operation. In this case. For bounded chemistries. it is also optimal from a selectivity point of view to maximize the per pass conversion of one or more species. If there is a significant change in the production rate. Figures 6 and 7 show the optimization landscape for chemistry 6. a supervisory control structure may be necessary. Because this ′ chemistry is reactor-volume bounded. the reactor volume constraint will “sweep” the optimal operating point to higher temperatures (and recycle flow rates).2. Eng.0 (2-EA. However. the byproduct ′ production rate will decrease with increasing temperature when the reactor is operated completely full at all times. However.1 > 1. and the high and low-temperature constraints do not shift. Because EA. Reducing the reactor temperature will reduce the conversion of all species. because this chemistry is reactor-volume bounded. then the reactor volume constraint may become active. Bounded Chemistry. we can write PD ) k1 ′ ′ V′ ) RA ′ q′ (23) (24) e1/T′ q′ RA ′ Again. with EA.. Before the production rate increase (Figure 6). low reactor temperatures will minimize the ′ reaction rate constant ratio k1. the optimal operating point lies on the minimum reactor temperature constraint. The optimum lies at the intersection of the high-temperature constraint and the reactor volume constraint for all production rates. before and after a produc′ tion rate increase. As before. which is unlikely. There are no obvious process variables that can be kept constant to ensure most profitable process operation when the production rate is changed. Figures 8 and 9 show the optimization landscape before and after a production rate change. Both the reactor temperature and reactor holdup should be kept constant at their maximum allowable values.0. bounded chemistry). it is not immediately clear what the optimal policy should be with regard to the reactor temperature.
Chlorination is often employed to introduce reactive sites on organic molecules.1 ′ (Vmax)-(n-m)/m ′ T′ n-m exp (q′)n-m(q′)m-n (43) mT′ ) n ′ . being first-order each in the concentration of catalyst (stannic chloride. 1. Silberstein et al.1 n > EA. A consequence of operating the process near to this limit is that PD .0 exp PD ) k1.1)/T′ ′ ′ e ′ PD ≈ Vmax ′ EA.EA. a reactor with this chemistry should be operated on the low-temperature bound iff ′ RA ≈ and e Vmax ′ 1/T′ EA. We follow previous analysis to obtain PC ) k0. 1 and q′ ≈ 1. Case Study: Benzene Chlorination This section presents results from a case study based on a process to produce chlorobenzene. Dichlorobenzene has no value and must be disposed of safely. using the same values for dimensionless groups (EA. Vol. The shape of the cost contours ′ ′ and reactor volume constraint are qualitatively quite similar to those of Figure 8 over the domain 0 < RA < ′ 1.EA.1 (RA)n(q′)-nV RT ) ) ) (38) (39) benzene + Cl2 f chlorobenzene + HCl (47) chlorobenzene + Cl2 f dichlorobenzene + HCl (48) These reactions can be carried out in the liquid phase at temperatures between 25 and 70 °C. as before.0) as in Figure 8. to maximize selectivity. Because the catalyst Dividing eq 39 by eq 38 gives ′ ′ PD ) k1. 17. In this case care must be taken to minimize the production of higher chlorinated benzenes. the case study is expanded to consider the situation involving nonisothermal reactor operation..1.1 . No.EA. and then presents new results for the nonisothermal case. Chem. and benzene (or chlorobenzene).0 exp T′ ( ( ) ) (44) e1/T′ V′ ≈ RA ′ and. 0exp - ( ( EA. The reactions are Figure 10 shows the optimization landscape for chemistry 8.Ind. The benzene chlorination process was the subject of a previous case study by Ward et al. Eng.13 report kinetic data for these reactions. 44. 1 is valid ′ over this region. For example. 2005 6735 consider chemistry 8 Vmax ) exp ′ desired (29) A + C f 2C A+AfD then r0 ) k0[A][C] r1 ) k1[A]2 1 (T′)(R ′) A -m (q′)m (41) undesired (30) ′ Solving this expression for RA with the assumption that the reactor holdup is at its maximum value gives ′ RA ) (Vmax)-1/m exp ′ ′R ′ P D ) k1 A V′ ) e1/T′ 2 e1/T′ q′ ) (R ′ + 1 + 2PD 2 ′) RA ′ RA A ′ (31) (32) 1 (mT′)q′ (42) And substituting this result into the expression for the byproduct production rate (eq 40) yields PD ) k1.1 > EA.1 ′ (RA n-m(q′)m-n ′) T′ (40) .0 m (34) not (45) k1. Therefore ′ ( 1 .1 Here.0 exp ′ ′ where it is assumed for the last equality that the mass density of all species is the same. SnCl4). More details are provided in the Supporting Information.3 ( 1 .1 >1 EA. without the simplifying assumption of eq 33. Therefore as a simplifying assumption.0 (35) (46) Otherwise it should be operated on the high-temperature bound. Res. This section first reviews the previous results for the isothermal case.0 exp Also from Section 2. The kinetic rate expressions they suggest are third-order overall. one route in the production of phenol (C6H5OH) from benzene is via the intermediate chlorobenzene (C6H5Cl).0 (2-EA. Now consider the general chemistry AfC AfD r0 ) k0[A]m r1 ) k1[A]n desired undesired (36) (37) where n > m for a bounded chemistry and EA. we can write (33) Therefore. Description of the Process.1 m ′ ′ (Vmax)(m-n)/m ′ PD ) k1. the optimal operating policy will have RA as small as possible. chlorine. we consider the case that RA ′ .0 and m and n are not necessarily integers.0 (RA)m(q′)-mV RT EA. which suggests that the approximation RA . Because this chemistry is reactor-volume bounded. 4. 4. k0.
Another consequence is that the optimal recycle flow rate has been reduced by 50%. With these assumptions.6736 Ind. Again as expected. it is assumed that these parameters are fixed and not available as degrees of freedom: [SnCl4] ) 0. In contrast. and EA. the recycle flow rate of benzene RB. In this case. × marks the optimal operating point.. Therefore. corresponding to a loss of 7. where the economic potential of the process is $494 000/year and the reactor holdup is at 34% of the maximum value. There is a lower bound on the reactor temperature that is determined by the minimum temperature difference required for heat exchange with the cooling water: T g 308 K (T g 35°C). because this value reflects the additional cost for oversizing the process equipment. 0e-Ea. As is sometimes the case for nonbounded chemistries. Eng. a loss of nearly 30% compared to the maximum achievable economic potential. the reaction rates are given by r0 ) k0 [benzene] r1 ) k1[chlorobenzene] k0 ) k0. the process has two operational degrees of freedom. in which case the process has a single degree of freedom. × marks the optimal operating point. the economic potential of the process is significantly reduced.39 × 105 min. The process was designed according to the methods of Douglas.14 The process flow diagram at level 4 in Douglas’ hierarchy is shown in Figure 11.-1. their values do not influence the selectivity-conversion profile. This operating point corresponds to a reactor holdup of 72% of the maximum value. there is a maximum in the economic potential function. The difference is that with this relative magnitude of reaction rate constants. This is a different result from the case where a process with the same chemistry and the same values of the activation energies is operated isothermally. which requires the greatest . In this case. Because the activation energy of the undesired reaction is greater than the activation energy of the desired reaction and the process chemistry is nonbounded. Chem.0/RT k1 ) k1.7 kJ/mol. The vertical dashed lines show the reactor volume constraint (on the left) and the recycle capacity constraint (on the right).3.1 ) 42. k1.1. at 202 kmol/hr. inferior operating policy would be to operate with the reactor completely full. The economic potential of the process with this inferior operating policy is $2. in the nonisothermal case it is beneficial to operate at the lowest possible temperature.8 kJ/mol. The economic potential of the process at this point is $3. and the optimization landscape can be represented using a contour plot diagram.6 million/year if it is operated with the reactor completely full.1/RT (49) where k0. Now we consider the case where the reactor temperature also can be adjusted. Figure 12. Process flow diagram for benzene chlorination.. the optimal operating point lies on the recycle capacity constraint. Because much less product is being produced. we expect the reactor volume constraint not to be active. 17. Figure 14 shows the optimization landscape for the case where the process is operated at 50% of the base case production rate. Res. Vol. the design and operation of the benzene chlorination process has assumed that the reactor will be operated at a constant temperature T ) 333 K. EA. the process incurs a loss of $1. 4. 44.030 mol/L and [Cl2] ) 0. Now consider a decrease in the production rate of 50%. An alternative.15 4.0 ) 34. The process is within the region of operation where the optimal operating policy is to scale the reactor holdup and recycle flow rate linearly with production rate. The solid line shows the operating economic potential of the flexible process as a function of the single operational degree of freedom. at 290 kmol/h. The distillation columns were designed and costed using the methods of Doherty and Malone. Note that this is somewhat less than the maximum achievable economic potential at the design stage. Up to this point. the location of the maximum has shifted now that capital costs are fixed. Results: Isothermal Operation.25 mol/L.0 ) 2. Results: Nonisothermal Operation. Optimization of the flexible benzene chlorination process after production rate decrease of 50%.2 million/year. and lies outside the feasible region.3% relative to the maximum achievable economic potential. concentration and chlorine concentration influence both reaction rates in the same manner. However. The operating economic potential of the plant after it has been built includes the fixed capital cost associated with the process equipment as well as the variable operating costs.2. it is expected (based on the analysis of Ward et al.30 × 105 min. the recycle flow rate of benzene. The optimization landscape is shown in Figure 13. 2005 Figure 11. No. The economic potential of the process when it is operated on the recycle capacity constraint is $458 000/year. where either the reactor low-temperature constraint or the reactor volume constraint is active.0e-Ea.1 million/year. Optimization of the flexible benzene chlorination process at the nominal production rate of 50 kmol/h. and now lies within the process constraints.0 ) 2. Figure 13. Figure 12 shows the optimization landscape for the process after it has been built.1) that the reactor should be operated at the lowest possible temperature.
then the recycle flow rate constraint can shift from active to inactive. Figure 16. This constraint switch is the last one that can take place for a chemistry of this type as the production rate is increased. No. its value must be determined by solving a nonlinear optimization problem.65PC h PC ) 0. 44. Summary of Figures 12-16 figure 12 13 14 15 16 a conditions PC ) PCa h PC ) 0. Table 4. 2005 6737 Figure 14. because the benzene chlorination chemistry is nonbounded. T ) 60 °C. These results are exactly consistent with the derived heuristics for optimal plantwide operation given in Table 2. Finally. Description of the Process. × marks the optimal operating point. Optimization landscape for benzene chlorination process at 65% of the nominal production rate. At this production rate. Figure 15 shows the optimization landscape when the production rate is at 65% of the nominal value. MTBE has been detected in the groundwater in many communities. 17. Optimization landscape for benzene chlorination process at 80% of the nominal production rate. 4. Full details are available in a web-published supplement to this document. Case Study: Novel High Molecular Weight Ethers for Gasoline Blending This section presents results from a case study based on a process to produce 2-methoxy-2-methylheptane. Optimization landscape for benzene chlorination process at 50% of the nominal production rate. × marks the optimal operating point. but the reactor holdup constraint is inactive as is usually the case for nonbounded chemistries. the process should be operated at the reactor volume constraint (or the lowtemperature constraint) for the purpose of achieving low temperature even though it is not beneficial to operate with the greatest possible per-pass conversion of reactant species.1. Figure 16 shows the optimization landscape when the production rate is at 80% of the nominal value. but the high temperature constraint is always inactive. At this production rate. Res. Thus. Eng. RB ) RB. and/or the recycle flow rate constraint may be active.. This situation is reflected in Figure 14 by the location of the optimal operating point X on the low-temperature constraint and away from the reactor volume constraint. As the production rate is further increased.max none T ) Tmin V ) Vmax V ) Vmax. it is not possible to cool the reactor all the way to the low-temperature constraint without violating the reactor volume constraint. the active constraint has shifted from reactor temperature to reactor holdup. it is possible to reduce the reactor temperature to the minimum value without violating the reactor holdup constraint.max Note: PC ) 50 kmol/hr.5PC h PC ) 0. h h Figure 15. it remains optimal to operate the process at the intersection of these constraints until the feasible region shrinks to zero and the process is no longer operable. 5. the reactor volume constraint. methyl tert-butyl ether (MTBE) was thought to be a valuable additive for this purpose. This circumstance is reflected in the figure by the optimal operating point now situated on the reactor volume constraint. Because the activation energy of the undesired reaction is greater than that for the undesired reaction. Chem. Therefore. Vol. The optimal recycle flow rate is still away from the constraint.4.5PC h PC ) 0. Alkyl ethers are used as fuel additives in gasoline to improve combustibility and octane number and to meet legislative requirements for oxygenate content. 5. Since its introduction.8PC h T ) Ta h T)T h T ) variable T ) variable T ) variable active constraints RB ) RB. However. × marks the optimal operating point.Ind.3 wt %. If the process is operated isothermally. Therefore the optimal operating point lies at the intersection of the reactor volume constraint and the recycle flow rate constraint. Now consider how the operation of the process should change as the production rate is increased from this point. possible reactor holdup. In the early 1990s. Case Study Conclusions. the optimal recycle flow rate has shifted to sufficiently high values that the recycle flow rate constraint is active. Because the production rate is small (50%) compared to the nominal production rate. one critical drawback of MTBE is that it is moderately soluble in water: 4. . Table 4 summarizes the process conditions and active constraints illustrated in the optimization landscapes presented in this case study. when the process is operated with variable reactor temperature both the reactor low temperature constraint.
so one possible way of overcoming this drawback is to use ethers with a higher molecular weight. The optimal operating point is marked with an “O”.14 million/year.1 ) 102.41 million/ year.5 × 1011 mol/(kg cat s) k1. but there is no incentive to go beyond this value. 17. as expected based on the analysis in this paper (Table 2) for most bounded chemistries with EA. that it is best to operate the reactor at the high-temperature constraint. Table 5.1 × 1011 mol/(kg cat s) EA. which suppresses the undesired reaction by decreasing the concentration of the methanol. Figure 17) from 2-methyl-1-heptene (MH) and methanol. This situation is represented in the case study as a stream which is 80 mol % 2-methylheptane and 20 mol % 2-methyl-1heptene. and other states may follow.0e-EA. where A is methanol. The operating economic potential of the process at the optimal operating point is $2. The reason for this result is that increasing the reactor temperature allows for a greater per-pass conversion of the bounded species A. Krause and co-workers16-19 have investigated the kinetics of the production of high molecular weight ethers from C6 to C8 alkenes and C1 to C4 alcohols. If the production rate were increased.0.1 > EA. Because the perpass conversion of the alkene is fixed. such a reactor network is too complicated for the pedagogical purpose of this case study. Therefore. Recently. Therefore. The reactor volume constraint prohibits low temperatures and low recycle flow rates. The properties of the catalyst impose a hightemperature constraint: the catalyst cannot be used over 120 °C. The solubility of ethers in water decreases with increasing molecular weight. the process chemistry is effectively of the type A f C. The capacity of the separations system prohibits high recycle flow rates. 44. which suppresses the undesired reaction even though the ratio of the rate constants (k1/ k0) increases. the reactions are typically equilibrium limited and high conversion can be achieved by employing multiple reactors with distillation columns between to remove the desired product. Data reported by Krause and co-workers and/or data generated from the models suggested by Krause and co-workers were fitted to pseudo-homogeneous models of the form MH + MeOH f MMH r0 ) k0xMHxMeOH 2MeOH f DME + H2O r1 ) k1xMeOH2 k0 ) k0. but the optimal operating point would remain at the intersection of the reactor volume constraint and the upper reactor temperature constraint. while the operating economic potential at the base case design point is $2.21 However. it is usually best to operate the process at the highest possible temperature. C is the desired ether.0 ) 90 kJ/mol EA.6 kJ/mol Consequently. it is necessary to achieve an alkene conversion of approximately 90%. we consider the production of 2-methoxy-2-methyl heptane (MMH. Although the activation energy of the undesired reaction is greater than the activation energy of the desired reaction. The feasible operating region then is the region of space that is bounded by these curves. Figure 20 shows the byproduct production rate versus reactor temperature when the reactor is operated completely full. However it is clear from the contour plot. the reactions are assumed here to be kinetically limited over the range of conversion of interest. In this case study.20. it is necessary to operate the process at a higher temperature than the MTBE process. Figure 19 shows the economic optimization landscape. A requirement for the blending process is that the hydrocarbon stream contain no more than 2 mol % alkene. MTBE is being phased out as a gasoline additive in California. The location of the base-case design is marked with an “X”. but rather is fed along with the alkane to a downstream blending process. Results. Vol. The reason for this is that it is possible to achieve a higher conversion at higher temperatures. Values of Kinetic Parameters k0. higher molecular weight olefins are considerably less reactive than isobutene in etherification reactions. Unfortunately. and D represents undesired byproducts.0e-EA. Chem. As is the case for the MTBE process. the opposite of what would be expected on the basis of the activation energies of the reactions alone. Because of the difficulty of separating the alkane from the alkene.3. Both of these considerations will tend to promote the undesired reaction and make selectivity losses a greater concern. the feasible region would shrink. unconverted alkene is not separated and recycled back to the reactor.. The optimal operating point is always at the intersection of the reactor volume constraint and .0 ) 2. and with a molar excess of methanol. These values are representative of typical properties of commercial acid resin catalysts such as Amberlyst. the bounded species. 5. 2005 MH + H2O f MHOH r2 ) fast (50) Figure 17. 5. selectivity nevertheless improves when the process is operated at higher temperatures. Figure 18 shows the process flow diagram at Douglas’ level 4.0/RT k1 ) k1. Res. It is assumed that the acid resin catalyst employed in these reactions costs $10/kg and will deactivate at temperatures above 120 °C. All of the process constraints are shown as dashed lines. They generally develop sophisticated kinetic models for these types of reactions based on the activity of the species in solution and assuming either a Langmuir-Hinshelwood or Eley-Rideal type reaction mechanism. No. Kinetic data are taken from papers by Krause and co-workers cited earlier. The values of the parameters are given in Table 5.0 ) 7. Case Study Conclusions.1/RT where x is the mole fraction of species. A + A f D. Therefore. It is assumed that the hydrocarbon feed to the process is a mixture of alkenes and alkanes.6738 Ind. the etherification chemistry is a bounded chemistry. This case study also illustrates results which are summarized in Table 2. which is the opposite of what would be expected on the basis of the activation energies alone. For a bounded chemistry with the activation energy of the undesired reaction greater than that of the desired reaction. which would correspond to a loss of 11% relative to the greatest possible economic potential. 2-methoxy-2-methylheptane. To achieve this high conversion with a reasonable reactor residence time.2. Eng.
2005 6739 Figure 18. × marks the design operating point. one could argue that if pilot plant data suggest that selectivity is increasing with conversion. Figure 20. Appendix A. then the chemistry is bounded. It is shown that the optimal reactor temperature operating policy in the plantwide context is sometimes radically different from what conventional wisdom based on reactor design would suggest. Byproduct production rate vs reactor temperature along the reactor volume constraint. coupled with good engineering judgment. This heuristic. O marks the optimal operating point. As a heuristic. The reason for this is that it is possible to obtain analytical results in this case whereas it is not possible to obtain analytical results in many other cases. Vol. Eng. and even the case where the only information available about the process chemistry is the stoichiometry and some selectivity-conversion data from a pilot plant or laboratory experiment. Conclusions This paper presents an analysis of the problem of determining the optimal plantwide operating policy for plants with recycle. gas-phase reactions.. when reactor temperature is also available as a degree of freedom. more complex reactor networks. and almost all of the analysis has been limited to the case where the reactor network consists exclusively of a single ideal CSTR. Etherification process at Douglas14 level 4. 44. The case of multiple undesired reactions could be the subject of a separate paper. Process chemistries are classified as bounded or nonbounded and as having dimensionless ′ activation energy EA. 6. What are here termed “bounded” chemistries constitute a subset of all chemistries for which selectivity increases with conversion for at least one reactant species. could be used to extend the results developed in these papers to many other. On the basis of this classification. If the optimal point of operation of the process is always at the intersection of the same constraints. processes are assigned an operating policy that is defined in terms of the constraints that are active. then it is straightforward to design a self-optimizing control structure: the process should be controlled so that those constraints are always active. and what are here termed “nonbounded” chemistries constitute a subset of all chemistries for which selectivity is decreasing with conversion for all reactant species. Chem.1 greater than or less than one. Res. Figure 19. However we present here just a few comments and observations about that situation. It is worthwhile to consider how the insight which is developed from this simple case could be applied to other cases. such as nonhomogeneous kinetics. All of the analysis presented in this paper and the one which preceded it has focused on liquid-phase reactions with pseudo-homogeneous kinetics. No. The analysis also provides insight as to whether it may be possible to design a self-optimizing control structure for the process. By contrast. if constraints shift during operation it may be difficult to design a self-optimizing control structure. Multiple Recycled Species and Multiple Undesired Reactions All of the results presented in this paper are for the case of a single undesired reaction. or may switch during the course of operating the process. more complicated cases and in particular to reaction systems where a formal kinetic rate expression is not available.Ind. whereas if it is decreasing then the chemistry is nonbounded. 17. Such a process is a good candidate for self-optimizing control. the high temperature constraint. because the process can be kept at its economic optimum simply by controlling the reactor holdup and reactor temperature so that they always lie on their constraints. All of the framework and methodology presented in this paper and . Optimization landscape for the etherification process with reactor volume constraint. inactive.
1 > 1. 8. Eng. S. I. (9) Monroy-Loperena. Mahajanam. Nomenclature C ) cost ($/h) CP ) cost associated with stream P ($/mol) kn ) reaction rate constant for reaction n k0.. 1998. With multiple undesired reactions. (17) Karinen. Res. Res.. Eng. 2004. 487.. Alvarez-Ramirez. 42. J. 366. A. 2000.. Diss.i > 1. M. Balanced Control Scheme for Reactor/Separator Processes with Material Recycle.i < 1 or ′ ′ all EA. I. J. V. Automatica 1970. A. If the point of ′ maximum selectivity lies between the minimum and maximum temperature constraints.n ) Arrhenius pre-factor for reaction n EA. L. A. 43. respectively. Verlagsgesellschaft: Weinheim. 33. 51. Chem. 1999. 10. I. (18) Kiviranta-Paakkonen. Neumeister. Eng. (16) Karinen. H. Conceptual Design of Distillation Systems. 63. 20. (7) Wu. 6. R. Snowball Effects in Reactor/Separator Processes with Recycle... Ind. S.. W. R. Ind. Mellichamp. S. 1988. When multiple recycled species are involved and reactor temperature is variable.6740 Ind. Supporting Information Available: More details regarding a process to produce chlorobenzene. (5) Larsson. Yu. 247-256. A. Hydrocarb. Res. A. Chem. Dehydration of the Alcohol in the Etherification of Isoamylenes with Methanol and Ethanol. Govatsmark. C. M. Chem.. Chem. F. Chem.. 209.. H. D. (21) Scholz.. J. (20) Bitar.. 45. C. S. 2005 Accepted May 16. Ind. O. Yu.. C. Krause. F. Krause. O. L. 3957. 63-66. Hazbun. F. there are multiple EA. AIChE J. Control Structure Selection for Reactor. Skogestad. C. Control 2000.. R. Res. A-gen. Luyben. Helsinki University of Technology.acs.. Process. 2005 IE0491589 . 1853. then the process chemistry falls into the ′ same classification as EA. (6) Larsson. Ward et al. 2005 (2) Fogler. S. Douglas. Appl. Skogestad. (15) Doherty.. Etherification of Some C8 Alkenes to Fuel Ethers Sc.. L. J. Comput. O. (4) Luyben. F.org. 2001. This material is available free of charge via the Internet at http://pubs. Reactor/ Separator Processes with Recycles. J. 401. S. Reactor/Separator Processes with Recycle. K. L. L. A. A. 1984. Piel.. McGraw-Hill: NewYork. Chem. (14) Douglas. 3rd ed. MTBE production and economics. Ind.n ) activation energy for reaction n P ) production rate of species (mol/h) q ) reactor effluent volumetric flow rate (L/h) r ) specific reaction rate [mol/(L h)] R ) recycle flow rate (mol/h) vA ) molar volume of species A (L/mol) V ) reactor volume (L) Literature Cited (1) Ward. 1990.-2. Candidate Control Structures for Operability. K. Methyl Tert-Butyl Ether. A. Chem. B. 2002. K. and if the process chemistry is nonbounded. 18-24.1 > 1.. if it ′ lies below the minimum temperature constraint. if the process chemistry is bounded. (8) Wu.. John Wiley and Sons: New York 1999. 1225. 21. 81-87. Ullmann’s Encyclopedia of Industrial Chemistry. S. Struckmann. Skogestad. Eng. M. J. 3rd ed. J. Res. 43. 299. In this situation. Reactivity of some C8-alkenes in Etherification with Methanol. Eng. O. Fundam. Chem. Received for review September 3. then the activation energy of the desired reaction is between the activation energies of the undesired reactions. However. Germany. E. (3) Levenspiel. H. A. Eng. 1969. Rijnsdorp. then the process behaves as if EA. Linnekoski.. 188. Eng. 1996. In general. K. T. Vol.. Doherty. 37. Elements of Chemical Reaction Engineering. Etherification of C5 and C8 alkenes with C1 to C4 alcohols.. 17. Bliss. 2003.. Catal. (11) Skogestad. J. Importance of Process Chemistry in Selecting the Operating Policy for Plants with Recycle. If this point lies above the maximum temperature constraint. J.. p 543550.-A Review and a New Design Procedure. W. (19) Karinen. 27. ′ ′ If some EA. 10. No. Butzert. one for each undesired reaction.. M. P. Nierlich. L. Constraint Control on Distillation Columns. Ind. i.. if even one reactor volume bounded species is present (which means that the overall process chemistry is classified as bounded) then it is usually optimal to maximize the per-pass conversion by maximizing the reactor holdup and reactor temperature. Chem. 44. Eng. these constraints may shift depending on the production rate. Otherwise.. 1994.-1. 2001..i. D. Process Contr. R. Model Ident. then the optimization landscape cannot be represented on a contour plot. (13) Silberstein. S. E. Plantwide control: the search for the self-optimizing control structure. J. Comput.1 < 1. Separator and Recycle Processes. Res. Malone. B.i > 1. R. (10) Maarleveld. 1291. J. 2004 Revised manuscript received May 4. Ind. then the process behaves as if EA. M. W. it may be optimal nevertheless to operate at the highest possible temperature in order to suppress one or more of the undesired reactions by maximizing the per-pass conversion of the bounded species. (12) Zheng. Prentice-Hall: Upper Saddle River. 1999.. Design for Composition Control. 2004. C. Plantwide Control.e. R. S. Solar.1 can be generalized to the case of multiple undesired reactions.. Lett. Finland 2002.. Eng. Yu. it is wellknown from reactor design that there is an intermediate temperature which balances the losses from the reactions and represents the point of maximum selectivity. Krause. NJ 1999.. Espoo. Linnekoski. 1255. B. T. C. the benefit of classification of chemistries as bounded or nonbounded is clear. Catal. 76. If all EA. Butt. Kinetics of Homogeneously Catalyzed Gas-Liquid Reactions: Chlorination of Benzene with Stannic Chloride Catalyst. Conceptual Design of Chemical Processes.i < 1 and some EA.1 < 1 or EA. Hierarchical Procedure for Plantwide Control System Synthesis. Chemical Reaction Engineering.. then it is generally desirable to operate at a temperature between the constraints. M. D.. McGraw-Hill: New York.
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